Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
  • A61K8/41—Amines
  • A61K8/418—Amines containing nitro groups
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
  • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/10—Preparations for permanently dyeing the hair

Definitions

• the present invention relates to a new process for the preparation of nitroanilines, to the use of these nitroanilines in dyeing compositions for keratin fibres, and in particular for human hair, and to the new nitroanilines prepared by this process.
• the present invention relates more particularly to a process for the preparation of compounds of the general formula: ##STR6## in which R denotes hydrogen, alkyl, alkyl substituted by one or more OH groups, alkoxyalkyl, or aminoalkyl of the formula: ##STR7## in which R 1 and R 2 can be identical or different and denote hydrogen, alkyl or alkyl substituted by one or more OH groups, and their salts
• the process according to the invention makes it possible to prepare the compounds of the formula (I) with an improved yield by reacting an amine RNH 2 , in which R has the meaning indicated above, with 3,4-methylenedioxynitrobenzene.
• This process is particularly valuable by virtue of the ease with which it can be carried out, since it involves only one step, and by virtue of the purity of the products which can thereby be obtained.
• 3,4-methylenedioxynitrobenzene is desirably heated in an excess of amine of the formula RNH 2 .
• the operating conditions such as temperature and reaction time, vary according to the nature of the amine used.
• the temperature is preferably from 70° to 170° C. and the reaction time is suitably 1 hour to 30 hours.
• R denotes hydrogen
• 3,4-methylenedioxynitrobenzene is desirably heated, in an autoclave, in a mixture of ammonia and a non-alcoholic solvent, such as an alkylene glycol ether. After precipitation of the unreacted initial product, filtration and neutralisation with hydrochloric acid, the acetyl derivative can be obtained, which, after acid hydrolysis and neutralisation of the reaction medium, leads to the desired product.
• the compounds more particularly prepared according to the invention are those in which R denotes an unsubstituted or hydroxy, alkoxy or amino-substituted alkyl group having 1 to 4 carbon atoms.
• R denotes an unsubstituted or hydroxy, alkoxy or amino-substituted alkyl group having 1 to 4 carbon atoms.
• R denotes an unsubstituted or hydroxy, alkoxy or amino-substituted alkyl group having 1 to 4 carbon atoms.
• R denotes an unsubstituted or hydroxy, alkoxy or amino-substituted alkyl group having 1 to 4 carbon atoms.
• the salts are preferably in the form of the hydro
• This process is essentially characterised in that an amine of the formula R 1 NH 2 , in which R 1 denotes a group --CH 2 CH 2 OH or --CH 2 CHOHCH 3 , is reacted with 3,4-methylenedioxynitrobenzene by heating 3,4-methylenedioxynitrobenzene in an excess of amine of the formula R 1 NH 2 , at a temperature of, say, 70° to 170° C., for, say, 1 to 30 hours, in that a dilute solution of hydrochloric acid is added to the crude reaction product obtained, in that the product insoluble in the hydrochloric acid medium is filtered off, in that it is purified to give a compound of the formula: ##STR14## in that the mother liquors from filtration are rendered alkaline with a solution of sodium hydroxide, in that the product which precipitates in the sodium hydroxide medium is isolated and purified, the said product corresponding to the formula: ##STR15##
• the product insoluble in the dilute hydrochloric acid medium can be separated off and washed and then treated with a dilute solution of sodium hydroxide.
• the fraction insoluble in the sodium hydroxide medium which consists of the unreacted initial product, can then be removed by filtration.
• acidification of the filtrate the product of the formula (IIA) can be obtained virtually pure.
• the product precipitated from the mother liquors arising from filtration, which have been rendered alkaline, can be obtained after the mother liquors have first been cooled to 0° C.
• the precipitate is filtered off, washed with water and dried.
• These compounds can also be prepared in the form of their salts, such as the hydrochloride, hydrobromide or sulphate.
• the compounds prepared according to the invention are particularly suitable for use in dyeing compositions for keratin fibres, in particular for human hair.
• the dyeing compositions for keratin fibres, and in particular for human hair, according to the present invention are essentially characterised in that they contain at least one dyestuff corresponding to the formula: ##STR17## in which R' denotes an alkyl group, a group ##STR18## a polyhydroxyalkyl group, an alkoxyalkyl group or an aminoalkyl group of the formula: ##STR19## in which R 1 and R 2 , which are identical or different, denote hydrogen, alkyl or monohydroxyalkyl or polyhydroxyalkyl and n is an integer from 2 to 4, or of the formula: ##STR20## in which R 1 denotes the group --CH 2 CH 2 OH or --CH 2 --CHOH--CH 3 and A denotes the group --OCH 2 CH 2 -- or ##STR21## or mixtures thereof, or a cosmetically acceptable salt of these compounds.
• compositions according to the invention which contain at least one compound corresponding to the formula (III) or (IIB), in a cosmetically acceptable solvent medium, can be used for the direct dyeing of keratin fibres or in the oxidation dyeing of these fibres, in which case the compounds of the formula (III) or (IIB) impart a complementary sheen to the base coloration obtained by oxidative development of oxidation dyestuff precursors.
• compositions suitably contain the compound of formula (III) or (IIB) in an amount from 0.001 to 5% by weight, and preferably 0.01 to 3% by weight, relative to the total weight of the dyeing composition.
• compositions of the invention can contain anionic, cationic, non-ionic or amphoteric surface-active agents or mixtures thereof, and preferably cationic and/or non-ionic surface-active agents.
• surface-active products are suitably present in the compositions of the invention in an amount from 0.5 to 55% by weight, and preferably 2 to 40% by weight, relative to the total weight of the composition.
• the cosmetic vehicle generally consists of water; organic solvents can also be included in the compositions in order to solubilise compounds which would not be sufficiently soluble in water.
• organic solvents can also be included in the compositions in order to solubilise compounds which would not be sufficiently soluble in water.
• these solvents there may be mentioned lower alkanols (i.e. of 1 to 6, especially 1 to 4, carbon atoms), such as ethanol and isopropanol, polyols, such as glycerol, glycols or glycol ethers, such as 2-butoxyethanol, ethylene glycol, ethylene glycol monoethyl ether, propylene glycol, and diethylene glycol monoethyl ether and monomethyl ether, and mixtures thereof.
• These solvents are preferably present in amounts from 1 to 75% by weight, and in particular from 5 to 50% by weight, relative to the total weight of the composition.
• compositions can be thickened, preferably with sodium alginate, gum arabic, cellulose derivatives, such as methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose, and various polymers acting as thickeners, more particularly acrylic acid derivatives It is also possible to use inorganic thickeners, such as bentonite. These thickeners are preferably present in amounts of 0.5 to 10% by weight, and in particular 0.5 to 3% by weight, relative to the total weight of the composition.
• compositions according to the invention can also contain various adjuvants normally used in hair-dyeing sequestering agents, film-forming agents, buffers, perfumes, alkalising agents and acidifying agents.
• compositions can be presented in various forms, such as a liquid, cream or gel or any other form suitable for hair dyeing. Further, they can be packaged in aerosol cans in the presence of a propellant.
• the pH of these dyeing compositions is suitably 3 to 11.5 and preferably 5 to 10.5. It is adjusted to the desired value with an alkalising agent, such as ammonia, sodium carbonate, potassium carbonate or ammonium carbonate, sodium hydroxide or potassium hydroxide, alkanolamines, such as mono-, di- or tri-ethanolamine, 2-amino-2-methylpropanol or 2-amino-2-methylpropane-1,3-diol, or alkylamines, such as ethylamine, diethylamine or triethylamine, or with an acidifying agent, such as phosphoric, hydrochloric, tartaric, acetic, lactic or citric acid.
• an alkalising agent such as ammonia, sodium carbonate, potassium carbonate or ammonium carbonate, sodium hydroxide or potassium hydroxide
• alkanolamines such as mono-, di- or tri-ethanolamine, 2-amino-2-methylpropanol or 2-amino-2-
• compositions are intended for use in a process of direct dyeing of the hair, they can contain, in addition to the compounds according to the invention, other direct dyestuffs, such as azo dyestuffs, anthraquinone dyestuffs, for example tetraminoanthraquinone, aminoquinones, nitrobenzene dyestuffs other than those of formula (III) or (IIB), and, more particularly, the following compounds: 2-methyl-6-nitroaniline, 3-nitro-4-aminophenol, 3-nitro-4-N-( ⁇ -hydroxyethyl)-aminophenol, 3-nitro-4-amino-6-methylphenol, 3-amino-4-nitrophenol, 2-amino-3-nitrophenol, 2-amino-5-nitrophenol, 2-( ⁇ -hydroxyethyl)-amino-5-nitrophenol, 3-nitro-6-N-( ⁇ -hydroxythyl)-aminoanisole, 3-N-( ⁇ , ⁇ -dihydroxypropyl)-amino-4
• compositions are applied to the keratin fibres for, say, 5 to 70 minutes and the fibres are then rinsed, optionally washed and rinsed again, and dried.
• compositions can be also be used in the form of hair-setting lotions intended both for imparting a slight coloration to the hair and for improving its hold.
• they are generally presented in the form of aqueous, alcoholic or aqueous-alcoholic solutions containing at least one cosmetic resin, and they are applied to wet hair which has been washed and rinsed beforehand, which is optionally wound onto rollers and then dried.
• the cosmetic resins used in the setting lotions can be, in particular, polyvinylpyrrolidone, crotonic acid/vinyl acetate and vinylpyrrolidone/vinyl acetate copolymers, monoesters of maleic anhydride/butyl vinyl ether and maleic anhydride/methyl vinyl ether copolymers, as well as other cationic, anionic, non-ionic or amphoteric polymers normally used in this type of composition.
• These cosmetic resins are generally present in the compositions of the invention in amounts of 1 to 3% by weight, and preferably of 1 to 2% by weight, based on the total weight of the composition.
• compositions constitute oxidation dye formulations
• the compounds of the formula (III) or (IIB) are used essentially in order to impart a sheen to the final dyeing.
• compositions then contain oxidation dyestuff precursors in association with at least one nitro dyestuff of the formula (III) or (IIB).
• para-phenylenediamines such as: para-phenylenediamine, para-toluylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-dimethyl-3-methoxypara-phenylenediamine, N-( ⁇ -methoxyethyl)-para-phenylenediamine, 4-N,N-di-( ⁇ -hydroxyethyl)-aminoaniline, 4-(N-ethyl-N-carbamylmethyl)-aminoaniline and also their salts.
• para-phenylenediamines such as: para-phenylenediamine, para-toluylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-dimethyl-3-methoxypara-phenylenediamine, N-( ⁇ -methoxyethyl)-para-phenylenediamine, 4-N,N-di-( ⁇ -hydroxyethyl)
• para-aminophenols such as: para-aminophenol, N-methyl-para-aminophenol, 2-chloro-4-aminophenol, 3-chloro-4-aminophenol, 2-methyl-4-aminophenol and their salts.
• They can also contain heterocyclic derivatives, for example: 2,5-diaminopyridine and 7-aminobenzomorpholine.
• compositions according to the invention can contain couplers which are well known in the state of the art, in association with oxidation dyestuff precursors.
• Couplers which may be mentioned in particular are: meta-diphenols, such as resorcinol and 2-methylresorcinol, meta-aminophenols such as: meta-aminophenol, 2-methyl-5-aminophenol, 2-methyl-5-N-( ⁇ -hydroxyethyl)-aminophenol and 6-hydroxybenzomorpholine and their salts, ethanol, 2,4-diaminophenyl ⁇ -hydroxypropyl ether, 6-aminobenzomorpholine, 2-N-( ⁇ -hydroxyethyl)-amino-4-aminophenoxyethanol, 2,4-diaminophenyl ⁇ , ⁇ -dihydroxypropyl ether and their salts, and meta-acylaminophenols, metaureidophenols and meta-carbalkoxyaminophenols, such as: 2-methyl-5-acetylaminophenol, 2-methyl-5-ureidophenol and 2-methyl-5-carbethoxyaminophenol.
• couplers which can be used in the compositions of the invention: ⁇ -naphthol, couplers possessing an active methylene group, such as diketone compounds and pyrazolones, and heterocyclic couplers, such as 2,4-diamino-pyridine, and also their salts.
• these compositions may contain reducing agents, such as sodium sulphite, thioglycolic acid, thiolactic acid, sodium bisulphite, ascorbic acid and hydroquinone. These reducing agents are suitably present in amounts of 0.05 to 1.5% by weight, relative to the total weight of the composition.
• the oxidation dyestuff precursors are suitably present in the compositions of the invention at concentrations of 0.001 to 5% by weight, and preferably 0.03 to 2% by weight, based on the total weight of the composition.
• the couplers are also suitably present in amounts of 0.001 to 5% by weight and preferably 0.015 to 2% by weight.
• Their pH is preferably 7 to 11.5 and can be adjusted thereto with the alkalising agents mentioned above.
• the process for dyeing keratin fibres, in particular human hair, involving development with an oxidising agent consists in applying, to the hair, the dyeing composition comprising both a dyestuff according to the invention and dyestuff precursor, and in developing the coloration with an oxidising agent, which is either present in the dyeing composition or is applied to the hair in a second step.
• the oxidising agent is preferably hydrogen peroxide, urea peroxide or a per-salt.
• a solution of hydrogen peroxide of 20 volumes strength can be used in particular.
• composition has been applied to the keratin fibres with the oxidising agent, a period of 10 to 50 minutes, preferably 15 to 30 minutes, is generally allowed, after which the keratin fibres are rinsed, optionally shampooed and rinsed again, and dried.
• compositions which contain nitro dyestuffs of the formula (III) in which R' denotes alkoxyalkyl or a group of the formula: ##STR22## in which R 1 and R 2 and n have the meanings indicated above.
• the filtrate containing sodium hydroxide is washed twice in succession by extraction with 300 ml of chloroform and then, after cooling to 0° C., it is neutralised by adding hydrochloric acid of density 1.18.
• the expected product precipitates. It is filtered off, washed with water and then dried in vacuo.
• the filtrate is acidified to pH 2 with a 5N solution of hydrochloric acid in order to precipitate the 2-N-( ⁇ -hydoxyethyl)-amino-5-nitrophenol.
• the product is recrystallised from water and then dried.
• a solution of 0.18 mol (30 g) of 3,4-methylenedioxynitrobenzene in a mixture of 240 ml of 28% strength ammonia solution and 240 ml of diethylene glycol dimethyl ether is heated at 100° C. for 28 hours in an autoclave. After cooling, 480 ml of water are added. The unreacted initial product precipitates. It is recovered by filtration and the filtrate is then neutralised with hydrochloric acid. After filtration, the filtrate is extracted with ethyl acetate. The ethyl acetate is driven off in vacuo. The residue is treated with 25 ml of acetic anhydride and then kept in a boiling water-bath for 30 minutes.
• acetyl derivative After cooling, the expected product is isolated in the form of the acetyl derivative.
• the mother liquors from filtration, cooled to 0° C., are rendered alkaline to pH 10 with a 5N solution of sodium hydroxide.
• the filtrate is treated with 330 ml of hydrochloric acid of density 1.18, with stirring, so as to give a pH of 3.5.
• the expected product precipitates in the form of crystals. It is filtered off, washed with water and recrystallised from alcohol. After drying, 32 g of product are obtained. The melting point is 184° C. Yield: 36.3%.
• the mother liquors After the 2-N-( ⁇ -hydroxypropyl)-amino-5-nitrophenol phenol has been filtered off, the mother liquors, cooled to 0° C., are rendered alkaline to pH 10 with a 5N solution of sodium hydroxide and then saturated with sodium chloride, with stirring. The expected product precipitates. It is filtered off, washed with water and redissolved in 140 ml of a 0.5N solution of hydrochloric acid for the purpose of purification. After filtration to remove a small amount of insoluble material, this solution containing hydrochloric acid is extracted twice with ethyl acetate in order to remove a small amount of 2-N-( ⁇ -hydroxypropyl)-amino-5-nitrophenol. It is then rendered alkaline with ammonia solution. The expected product precipitates. It is filtered off, washed with water and recrystallised twice from alcohol. After drying in vacuo, it melts at 142° C.
• the extraction ethyl acetate is driven off in vacuo.
• the residual oil (12 g) is fractionated by chromatography on silica gel 60 (MERCK).
• the purified expected product is eluted with a toluene/ethyl acetate (60/40) mixture.
• the solvent is driven off in vacuo.
• this mixture When applied to bleached hair for 30 minutes at 30° C., this mixture imparts to the hair, after rinsing and shampooing, a coloration of 5 Y 7/10 according to the Munsell notation.
• this mixture When applied to bleached hair for 20 minutes at 30° C., this mixture imparts to the hair, after rinsing and shampooing, a coppery blond coloration.
• this mixture When applied to bleached hair for 25 minutes at 30° C., this mixture imparts to the hair, after rinsing and shampooing, a copper coloration with a purple sheen.
• this mixture When applied to bleached hair for 20 minutes at 30° C., this mixture imparts to the hair, after rinsing and shampooing, a coloration of 7.5 YR 6/10 according to the Munsell notation.
• a solution of 0.2 mol (39.6 g) of 3-nitro-4-N-( ⁇ -hydroxyethyl)-aminophenol in 104 ml of a 2.3N solution of sodium hydroxide (0.24 mol) is heated beforehand to about 100° C. and 0.24 mol (22.7 g) of 1-chloropropan-2-ol is then added thereto. After the reaction medium has been kept in a boiling water-bath for 2 hours, it is and with 0.12 mol (11.34 g) of 1-chloropropan-2-ol. The heating is maintained for a further 2 hours in the boiling water-bath. After cooling to 0° C., the medium is rendered alkaline to pH 9 with a solution of sodium hydroxide.
• the expected product crystallises and it is filtered off and washed with a normal solution of sodium hydroxide and then with water. After drying in vacuo at 60° C., it melts at 118° C. After recrystallisation from ethanol and recrystallisation from ethyl acetate, it melts at 122° C.
• Cemulsol NP4 Nonylphenol containing 4 mols of ethylene oxide, sold by Rhone Poulenc.
• Cemulsol NP9 Nonylphenol containing 9 mols of ethylene oxide, sold by Rhone, Poulenc.
• Cellosize WPO3 Hydroxyethylcellulose sold by Union Carbide.
• Lauramide Lauric acid monoethanolamide sold by Witco.
• Alfol C 16 / 18 Cetyl/stearyl alcohol sold by Condea.
• Lanette wax E Partially sulphated cetyl/stearyl alcohol sold by Henkel.
• Cemulsol B Oxyethyleneated castor oil sold by Rhone Poulenc.
• Carbopol 934 Acrylic acid polymer with a molecular weight of 2 to 3 million, sold by Goodrich Chem. Company.
• Trilon B Ethylenediaminetetraacetic acid.

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• 1982
  • 1982-08-24 DE DE3249986A patent/DE3249986C2/de not_active Expired - Lifetime
  • 1982-08-24 DE DE19823231455 patent/DE3231455A1/de not_active Ceased
  • 1982-08-25 GB GB08224393A patent/GB2104895B/en not_active Expired
  • 1982-08-25 IT IT68037/82A patent/IT1191211B/it active
  • 1982-08-25 CH CH5059/82A patent/CH658245A5/fr not_active IP Right Cessation
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• 1983
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• 1986
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• 1990
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• 1991
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